X-Ray Absorption Spectroscopy of Strontium(II) Coordination

Detailed analyses of crystalline, hydrated, and precipitated strontium compounds and an aqueous strontium solution by synchrotron extended X-ray absorption fine structure (EXAFS) were used to quantify local thermal and static disorder and to characterize strontium coordination in a variety of oxygen-ligated bonding environments. Analysis of anharmonic vibrational disorder (i.e., significant contribution from a third cumulant term (C(3)) in the EXAFS phase-shift function) in compounds with low and high static disorder around strontium showed that first-shell anharmonic contributions were generally not significant above experimental error in the EXAFS fits (R+/-0.02 ? with and without C(3)). The only case in which a significant apparent decrease in Sr-O distance was observed with increasing temperature, and for which a third cumulant term was significant, was for dilute strontium in aqueous solution. Empirical parameterization of Debye-Waller factor (sigma(2)) for strontium compounds as a function of backscatterer atomic number (Z), interatomic Sr-Z distance, and temperature of spectral data collection showed systematic increases in sigma(2) as a function of increasing temperature and Sr-Z bond length. At values of sigma(2) greater than approximately 0.025 ?(2) (for N<12 and R(Sr)-Z>3 ?), backscattering was generally not significant above noise levels in spectra of compounds of known crystal structure. Comparison of the EXAFS spectra of freshly precipitated SrCO(3) (spectra collected wet) to that of dry, powdered strontianite (SrCO(3)(s)) indicated no significant differences in the local atomic structure around strontium. Analysis of partially hydrated strontium in natural Ca-zeolite (heulandite) showed that strontium is substituted only in the calcium (Ca2) site. Backscattering from aluminum and silicon atoms in the zeolite framework were apparent in the EXAFS spectra at low and room temperature at distances from central strontium of <4.2 ?. Comparison of strontium structural coordination determined in this and previous studies suggests that previous EXAFS determinations of hydrated strontium may have underestimated first-shell interatomic distances and coordination numbers because minor contributions to the EXAFS phase-shift and amplitude functions were not accounted for, either theoretically or empirically. Copyright 2000 Academic Press.     

Biomembrane phospholipid-oxide surface interactions: crystal chemical and thermodynamic basis

Quartz has the least favored surface among many oxides for bacterial attachment and for lipid bilayer or micelle interactions. Tetrahedrally coordinated crystalline silica polymorphs are membranolytic toward liposomes, lysosomes, erythrocytes, and macrophages. Amorphous silica, the octahedral silica polymorph, (stishovite), and oxides such as Al2O3, Fe2 O3, and TiO2 are less cytotoxic. Existing theories for membrane rupture that invoke interactions between oxide surfaces and cell membrane phospholipids (PLs) do not adequately explain these differences in membranolytic potential of the oxides. The author presents a crystal chemical, thermodynamic model for the initial interaction of oxide surfaces with the quaternary ammonium component of the PL's polar head group. The model includes solvation energy changes and electrostatic forces during adsorption, represented by the dielectric constant of the solid and the charge-to-radius ratio of the adsorbing solute. The nature of oxide-solute interactions compared with oxide-water, solute-water, and water-water interactions determines the membranolytic activity of the oxide, where the solute is TMA+, the quaternary ammonium moeity. Significant membrane rupture, as on quartz, requires unfavorable adsorption entropy (DeltaS(ads,TMA+)<0) to maximize disruption of normal membrane structure and requires favorable Gibbs free energy of exchange between TMA+ and the ambient Na+ ions (DeltaG(exc,TMA+/Na+) = DeltaG(ads,TMA+)-DeltaG(ads,Na+)<0) to maximize the extent of membrane affected. For amorphous silica, DeltaS(ads,TMA+) >0, so disruption of structure is limited, even though G(exc,TMA+/Na+) is <0. Stishovite and other oxides have DeltaS(ads,TMA+) <0, but now DeltaG(exc,TMA+/Na+) is>0 at the acidic to circumneutral pHs of cellular and subcellular organelle fluids. The model predicts the correct sequence of membranolytic ability: quartz > or = amorphous SiO2 >Al2O3 >Fe2O3 >TiO2. The model thus explains the relatively poor adhesion of bacterial cells to quartz and the lack of quartz as a biomineral. It is proposed that one function of extracellular polymeric substances exuded by bacteria is to render mineral surfaces more hydrophilic.     

Nelumbo nucifera leaves as source of water-repellent wax: Extraction through polar and non-polar organic solvents

Nelumbo nucifera leaves are rich source of natural wax possessing super-hydrophobic properties. It provides protection to them from ecological turbulences and climatic wear and tear. In this study, various experiments have been conducted to observe the yield of extraction and the determination of various functional groups, which are present in natural wax, derived from Nelumbo nucifera leaves. The natural wax has been extracted from lotus leaves through non-polar (hexane) and polar (ethanol) solvent via different extraction methods. The superhydrophobic wax has been successfully extracted with hexane. Whereas, ethanol did not extract the water-repellent wax of lotus leaf. Considering the cumulative amount, i.e. (desired + undesired), the maceration shows the extraction of 2.9% (%w/w, through hexane) and 10.2% (%w/w, through ethanol), while it was found 2.5% (%w/w, cycle period 15 min) and 9.0% (%w/w, cycle period 26 min) respectively, in case of Soxhlet extraction technique. For this specific case of natural wax recovery from biomass (lotus leaf), the maceration (traditional method) resulted a little bit superior extraction yield in comparison to the Soxhlet extraction method for extraction of crude wax. In the case of non-polar solvent (hexane), an extraction yield of 1.97% (%w/w) through maceration method was observed while in the case of non-polar solvent (ethanol), an extraction yield of 1.62% (%w/w) through Soxhlet extraction was observed. The TLC analysis on both types of extracts was performed. For the detection of various hydrocarbon chains in the crude wax extracts, FTIR was also performed. Topography of wax surface and wax-coated waterproof fabric was compared through SEM.     

A note on ratio and product type estimators

Summary The use of ratio and product estimators for the mean of a finite population is well known. This paper proposes transformed estimators obtained through parametric linear combination of the ratio, or product, and the usual unbiased estimator of the mean for any sample design. To the first degree of approximation, the proposed estimators have smaller mean square error than that of the ratio, product and the usual unbiased estimator, for suitable choice of the parameter. The superiority of the proposed estimators over others for small samples has been studied empirically.     

Differential refractometry of molecular complexes: A reinvestigation

A modified plot method is used to calculate equilibrium constants of molecular complexes. This method (Sahai andSingh's plot) is compared with the method ofYoshida andOsawa.

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Differentielle Refraktometrie von Molekülkomplexen: Eine Neuuntersuchung (Kurze Mitteilung)

Zusammenfassung Eine modifizierte refraktometrische Methode zur Berechnung von Gleichgewichtskonstanten von Molekülkomplexen wird verwendet und diese mit der Methode vonYoshida undOsawa verglichen.

     

Artabotryols A – E,New Lanostane Triterpenes from the Seeds of Artabotrys odoratissimus

Six new lanostane triterpenes, artabotryols A, B, C1, C2, D, and E ( 1, 2, 3a, 3b, 4 , and 5 , resp.) have been isolated from the seeds of Artabotrys odoratissimus (Annonaceae). Their structures have been established as (3α,22S,25R)‐3‐hydroxy‐22,26‐epoxylanost‐8‐en‐26‐one ( 1 ), (3α,22S,25R)‐22,26‐epoxylanost‐8‐ene‐3,26‐diol ( 2 ), (3α,22S,25R,26R)‐26‐methoxy‐22,26‐epoxylanost‐8‐en‐3‐ol ( 3a ), (3α,22S,25R, 26S)‐26‐methoxy‐22,26‐epoxylanost‐8‐en‐3‐ol ( 3b ), (3α,22S,25R)‐3,22‐dihydroxylanost‐8‐en‐26‐oic acid ( 4 ) and (3α,7α,11α,22S,25R)‐3,7,11‐trihydroxy‐22,26‐epoxylanost‐8‐en‐26‐one ( 5 ) by spectroscopic studies and chemical correlations.     

The low frequency behaviour in high frequency capacitance–voltage characteristics due to contribution of band-to-band tunnelling and generation–recombination in Hg0.75Cd0.25Te MIS capacitors

Hg_1−xCd_xTe Metal–Insulator–Semiconductor (MIS) capacitors were studied both experimentally and theoretically to investigate the capacitance contributions due to band-to-band (btb) tunnelling and generation–recombination (gr) of carriers to inversion layer capacitance. A good fit to the data has been obtained by including the btb contributions rather than gr contributions.     

Study of levels in51Cr through51V (p,nγ) reaction

The low lying levels in⁵¹Cr have been populated by⁵¹V (p, ny)⁵¹Cr reaction. The angular distribution of the ground state electromagnetic transitions from 1165, 1353, 1479 and 1557 keV states have been measured. The results are compared with the Hauser-Feshbach model of the statistical theory of nuclear reactions. The spins for the levels at 1165, 1479 and 1557 keV are shown to be 9/2^?, 11/2^? and 5/2^? respectively.     

In-beam gamma-ray and electron spectroscopy following the75As(p,n)75Se reaction

The level scheme of⁷⁵Se has been studied through the⁷⁵As (p, n) reaction at proton energies from 1.5 to 5.0 MeV.γ-ray and internal conversion electron measurements were made using NaI (T1) and Ge(Li) detectors and a six-gap electron spectrometer. A proportional counter and a thin window NaI(T1) detector were used to detectγ-rays with energies less than 30 keV. The level scheme has been established by observing the thresholds of variousγ-rays and byγ-γ and e^?-γ coincidence measurements. New levels at 133.0, 293.2, 790.0, 953.0, 1020.8, 1184.3, 1198.5 and 1258.2 keV not observed in earlier (p, n) studies have been established. Conversion coefficients of most of the low-lying transitions have been determined. Angular distributions of some of theγ-rays were also measured and compared with the statistical model calculations. DefiniteJ ^π assignments have been made to most of the low-lying levels. Life-times of the 112.1, 133.0, 286.7 and 293.2 keV levels have been measured to be 0.69±0.12, 5.3±0.6, 1.35±0.15 and 31±2 nsec respectively. The reduced transition probabilities for various low-lying transitions have been determined and compared with recent calculations. The 1/2^? and 9/2⁺ levels hitherto unknown in this nucleus has been identified. The structure of the low-lying levels is discussed in terms of the existing models.